Surfactant-templated polymer films prepared from polyethylenimine (PEI), cetyltrimethylammonium bromide (CTAB), and octaethylene glycol monohexadecyl ether (C16E8) were examined and the effect of increasing the percentage of nonionic surfactant in the micelles measured using both surface and bulk-sensitive techniques. It was found that there is a strong interaction between CTAB and C16E8, although no interaction between the C16E8 and PEI was observed. Generally, increasing the percentage Of C16E8 in the micelles decreases both the thickness and degree of order in the films; however, it was observed, depending on the conditions, that films could still be formed with as little as 20% cationic surfactant. Experiments on the CTAB/Brij56/PEI system were also performed and these indicate that it is similar to the CTAB/C16E8/PEI system.